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Abstract:

A fluorinated polyester blend is prepared by melt blending a fluorovinyl
ether functionalized polyester with a non-fluorinated polyester. The
fluoroether functionalized polyester can be a homopolymer or a copolymer.
The blend is useful for preparing fibers, yarns, fabrics, garments,
carpets, and other shaped articles. The shaped articles exhibit durable
soil, oil, and water repellency.

Claims:

1. A blend composition comprising a first aromatic polyester selected
from the group consisting of poly(trimethylene terephthalate) (PTT),
poly(ethylene naphthalate) (PEN), poly(ethylene isophthalate),
poly(trimethylene isophthalate), poly(butylene isophthalate), mixtures
thereof, and copolymers thereof, and a second aromatic polyester in
contact therewith, wherein the second aromatic polyester is present in
the composition at a concentration; and, wherein the second aromatic
polyester comprises a molar concentration of fluorovinylether
functionalized repeat units represented by structure I ##STR00041##
wherein, Ar represents a benzene or naphthalene radical; each R is
independently H, C1-C10 alkyl, C5-C15 aryl,
C6-C20 arylalkyl; OH, or a radical represented by the structure
(II) ##STR00042## with the proviso that only one R can be OH or the
radical represented by the structure II; R1 is a C2-C4
alkylene radical which can be branched or unbranched; X is O or CF2;
Z is H or Cl; a=0 or 1; and, Q represents the structure (Ia)
##STR00043## wherein q=0-10; Y is O or CF2; Rf1 is
(CF2)n, wherein n is 0-10; and, Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF.sub.2.

2. The composition of claim 1 wherein the first aromatic polyester is
poly(trimethylene terephthalate).

3. The composition of claim 1 wherein the second aromatic polyester is
present at a concentration of 0.1 to 10% by weight.

4. The composition of claim 1 wherein the second aromatic polyester the
fluorovinylether functionalized repeat unit represented by Structure I is
dimethyl 5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy-
)propoxy)ethoxy) isophthalate.

5. The composition of claim 4 wherein the dimethyl
5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)-
ethoxy) isophthalate is present at a molar concentration in the range of
40 to 60 mol-%.

6. The composition of claim 1 wherein the second aromatic polyester the
fluorovinylether functionalized repeat unit represented by Structure I is
dimethyl 5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate.

7. The composition of claim 6 wherein the dimethyl
5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate is present at
a molar concentration in the range of 40 to 60 mol-%.

8. The composition of claim 1 wherein the first aromatic polyester is
poly(trimethylene terephthalate), the second aromatic polyester is
present at a concentration in the range of 1-3% by weight, wherein the
second aromatic polyester the fluorovinylether functionalized repeat unit
represented by Structure I is dimethyl
5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)-
ethoxy) isophthalate present at a molar concentration of 40-60 mol-%.

9. A process comprising combining a first aromatic polyester selected
from the group consisting of poly(trimethylene terephthalate) (PTT),
poly(ethylene naphthalate) (PEN), poly(ethylene isophthalate),
poly(trimethylene isophthalate), poly(butylene isophthalate), mixtures
thereof, and copolymers thereof, with a second aromatic polyester to form
a combination wherein the second aromatic polyester is present in the
combination at a concentration; heating the combination to a temperature
between the softening point of the first aromatic polyester and the
degradation temperature of at least one component of the combination to
form a viscous liquid mixture, and mixing the viscous liquid mixture
until it has achieved the desired degree of homogeneity; the second
aromatic polyester comprising a molar concentration of fluorovinylether
functionalized repeat units represented by structure I ##STR00044##
wherein, Ar represents a benzene or naphthalene radical; each R is
independently H, C1-C10 alkyl, C5-C15 aryl,
C6-C20 arylalkyl; OH, or a radical represented by the structure
(II) ##STR00045## with the proviso that only one R can be OH or the
radical represented by the structure (II); R1 is a C2-C4
alkylene radical which can be branched or unbranched; X is O or CF2;
Z is H or Cl; a=0 or 1; and, Q represents the structure (Ia)
##STR00046## wherein q=0-10; Y is O or CF2; Rf1 is
(CF2)n, wherein n is 0-10; and, Rf2 is (CF2)p,
wherein p is 0-10, with the proviso that when p is 0, Y is CF.sub.2.

10. The process of claim 9 wherein the first aromatic polyester is
poly(trimethylene terephthalate).

11. The process of claim 9 wherein the second aromatic polyester is
present at a concentration of 0.1 to 10% by weight.

12. The process of claim 9 wherein the second aromatic polyester the
fluorovinylether functionalized repeat unit represented by Structure I is
dimethyl 5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy-
)propoxy)ethoxy) isophthalate.

13. The process of claim 12 wherein the dimethyl
5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)-
ethoxy) isophthalate is present at a molar concentration in the range of
40 to 60 mol-%.

14. The process of claim 9 wherein the second aromatic polyester the
fluorovinylether functionalized repeat unit represented by Structure I is
dimethyl 5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate.

15. The process of claim 14 wherein the dimethyl
5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate is present at
a molar concentration in the range of 40 to 60 mol-%.

16. The process of claim 9 wherein the first aromatic polyester is
poly(trimethylene terephthalate), the second aromatic polyester is
present at a concentration in the range of 1-3% by weight, wherein the
second aromatic polyester the fluorovinylether functionalized repeat unit
represented by Structure I is dimethyl
5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)-
ethoxy) isophthalate present at a molar concentration of 40-60 mol-%.

Description:

RELATED PATENT APPLICATIONS

[0001] The present invention is related to U.S. patent application Ser.
Nos. 12/873,428, and 12/873,402, and patent applications corresponding to
docket numbers CL5045, CL5226, and CL5330.

FIELD OF THE INVENTION

[0002] The present invention is related to blends that are combinations of
an aromatic polyester with another aromatic polyester having one or more
fluoroether functionalized repeat units. The blend is suitable for use in
preparing polyester shaped articles, in particular fibers and yarns, that
exhibit improved soil resistance, oil resistance, and water resistance.
In particular, the blends are useful in preparing films, fibers, fabrics,
carpets, and rugs with enhanced soil resistance.

BACKGROUND

[0003] Soil resistance, stain resistance, and water repellency are long
standing problems in carpets and textiles. It has long been known to
apply fluorinated substances to the surfaces of carpet and textile fibers
in order to reduce the surface wettability by oils, water borne dirt, and
the like. Such topical treatments have been found to be fugitive, wearing
off after periods short compared to the lifetime of the textile or
carpet, and requiring reapplication, generally by the consumer or a
private contractor, and can result in spotty treatment, and overall
degradation in appearance.

SUMMARY OF THE INVENTION

[0004] The invention provides a blend composition comprising a first
aromatic polyester selected from the group consisting of
poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN),
poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof
selected from the group consisting of poly(trimethylene terephthalate)
(PTT), poly(ethylene naphthalate) (PEN), poly(ethylene isophthalate),
poly(trimethylene isophthalate), poly(butylene isophthalate), mixtures
thereof, and copolymers thereof and a second aromatic polyester in
contact therewith, wherein the second aromatic polyester is present in
the composition at a concentration; and, wherein the second aromatic
polyester comprises a molar concentration of fluorovinylether
functionalized repeat units represented by structure I

with the proviso that only one R can be OH or the radical represented by
the structure II; R1 is a C2-C4 alkylene radical which can
be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0005] a=0 or 1; and, Q represents the structure (Ia)

##STR00003##

wherein q=0-10; [0006] Y is O or CF2; [0007] Rf1 is
(CF2)n, wherein n is 0-10; [0008] and, [0009] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

[0010] In another aspect, the invention provides a process comprising
combining a first aromatic polyester selected from the group consisting
of poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate)
(PEN), poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof,
with a second aromatic polyester to form a combination wherein the second
aromatic polyester is present in the combination at a concentration;
heating the combination to a temperature between the softening point of
the first aromatic polyester and the degradation temperature of at least
one component of the combination to form a viscous liquid mixture, and
mixing the viscous liquid mixture until it has achieved the desired
degree of homogeneity; the second aromatic polyester comprising a molar
concentration of fluorovinylether functionalized repeat units represented
by structure I

with the proviso that only one R can be OH or the radical represented by
the structure (II); R1 is a C2-C4 alkylene radical which
can be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0011] a=0 or 1; and, Q represents the structure (Ia)

##STR00006##

wherein q=0-10; [0012] Y is O or CF2; [0013] Rf1 is
(CF2)n, wherein n is 0-10; [0014] and, [0015] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

[0016] In another aspect, the present invention provides a fiber or yarn
comprising a blend composition comprising a first aromatic polyester
selected from the group consisting of poly(trimethylene terephthalate)
(PTT), poly(ethylene naphthalate) (PEN), poly(ethylene isophthalate),
poly(trimethylene isophthalate), poly(butylene isophthalate), mixtures
thereof, and copolymers thereof, and a second aromatic polyester in
contact therewith, wherein the second aromatic polyester is present in
the blend composition at a concentration; and, wherein the second
aromatic polyester comprises a molar concentration of fluorovinylether
functionalized repeat units represented by structure I

[0021] Rf2 is (CF2)p, wherein p is 0-10, with the
proviso that when p is 0, Y is CF2.

[0022] In another aspect, the present invention provides a process
comprising extruding a melt comprising a blend composition through an
orifice having a cross-sectional shape, thereby forming a continuous
filamentary extrudate, quenching the extrudate to solidify it into a
continuous filament, wrapping the filament on a first driven roll heated
to a temperature in the range of 60 to 100° C. and rotating at a
first rotational speed, followed by wrapping the filament on a second
driven roll heated to a temperature in the range of 100 to 130° C.
and rotating at a second rotational speed; wherein the ratio of the first
rotational speed to the second rotational speed lies in the range of 1.75
to 3, and accumulating the filament; wherein the blend composition
comprises a first aromatic polyester selected from the group consisting
of poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate)
(PEN), poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof,
and a second aromatic polyester in contact therewith, wherein the second
aromatic polyester is present in the blend composition at a
concentration; and, wherein the second aromatic polyester comprises a
molar concentration of fluorovinylether functionalized repeat units
represented by structure I

with the proviso that only one R can be OH or the radical represented by
the structure II; R1 is a C2-C4 alkylene radical which can
be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0023] a=0 or 1; and, Q represents the structure (Ia)

##STR00012##

wherein q=0-10; [0024] Y is O or CF2; [0025] Rf1 is
(CF2)n, wherein n is 0-10; [0026] and, [0027] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

[0028] In another aspect, the present invention provides a fabric
comprising a plurality of filaments at least a portion of the filaments
comprising a blend composition comprising a first aromatic polyester
selected from the group consisting of poly(trimethylene terephthalate)
(PTT), poly(ethylene naphthalate) (PEN), poly(ethylene isophthalate),
poly(trimethylene isophthalate), poly(butylene isophthalate), mixtures
thereof, and copolymers thereof, and a second aromatic polyester in
contact therewith, wherein the second aromatic polyester is present in
the blend composition at a concentration; and, wherein the second
aromatic polyester comprises a molar concentration of fluorovinylether
functionalized repeat units represented by structure I

with the proviso that only one R can be OH or the radical represented by
the structure II; R1 is a C2-C4 alkylene radical which can
be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0029] a=0 or 1; and, Q represents the structure (Ia)

##STR00015##

wherein q=0-10; [0030] Y is O or CF2; [0031] Rf1 is
(CF2)n, wherein n is 0-10; [0032] and, [0033] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

[0034] In another aspect, the present invention provides a carpet
comprising a backing, a yarn tufted into the backing, and an adhesive
binding the yarn and the backing at the point of contact therebetween,
the yarn comprising filaments at least a portion of which the filaments
comprise a blend composition comprising comprising a first aromatic
polyester selected from the group consisting of poly(trimethylene
terephthalate) (PTT), poly(ethylene naphthalate) (PEN), poly(ethylene
isophthalate), poly(trimethylene isophthalate), poly(butylene
isophthalate), mixtures thereof, and copolymers thereof, and a second
aromatic polyester in contact therewith, wherein the second aromatic
polyester is present in the blend composition at a concentration; and,
wherein the second aromatic polyester comprises a molar concentration of
fluorovinylether functionalized repeat units represented by structure I

with the proviso that only one R can be OH or the radical represented by
the structure II; R1 is a C2-C4 alkylene radical which can
be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0035] a=0 or 1;

and, Q represents the structure (Ia)

##STR00018##

wherein q=0-10; [0036] Y is O or CF2; [0037] Rf1 is
(CF2)n, wherein n is 0-10; [0038] and, [0039] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] FIG. 1 is a schematic drawing of a melt spinning apparatus suitable
for use in making fibers and yarns according to embodiments of the
invention.

[0041] FIGS. 2a-d are schematic drawings of a loom and certain component
parts thereof, suitable for use in making fabrics according to
embodiments of the invention.

[0042] FIG. 3 is a schematic drawing of the melt spinning arrangement for
the production of the fibers and yarns of Example 1.

[0043] FIG. 4 is a schematic drawing of the press-spinning apparatus used
for the production of the fiber of Example 7.

[0044] FIG. 5 is a schematic drawing of the apparatus employed in Examples
9-12 to produce bulked continuous filament yarn suitable for use in
preparation of carpet.

DETAILED DESCRIPTION

[0045] The blend compositions disclosed herein comprise a first aromatic
polyester selected from the group consisting of poly(trimethylene
terephthalate) (PTT), poly(ethylene naphthalate) (PEN), poly(ethylene
isophthalate), poly(trimethylene isophthalate), poly(butylene
isophthalate), mixtures thereof, and copolymers thereof, and a second
aromatic polyester in contact therewith, wherein the second aromatic
polyester is present in the composition at a concentration; and, wherein
the second aromatic polyester comprises a molar concentration of
fluorovinylether functionalized repeat units represented by structure I,
as shown supra. The blend composition has utility for producing polyester
shaped articles, in particular fibers and yarns that exhibit
significantly improved soil resistance and water resistance compared to
shaped articles prepared from the first aromatic polyester alone. The
blend composition can also be used for forming molded articles of any
shape.

[0046] The desired effects of soil repellency, oil repellency, and water
repellency in shaped articles, in particular fibers and yarns, formed
from the blends depend upon the surface concentration of fluorine. It has
been found that surface concentrations of 1-5 atom-% of fluorine result
in desirable levels of repellency. A fiber or film prepared from the
blend composition exhibits orders of magnitude higher so-called "fluorine
efficiency" versus that of a fiber or film prepared from an unblended
fluoropolymer having the same surface fluorine concentration. Fluorine
efficiency, as used herein for a shaped article, is defined as the ratio
of the surface concentration of fluorine to the total concentration of
fluorine in the shaped article.

[0047] It has further been found that certain processes reduce fluorine
efficiency while others enhance it. For example, pressure dyeing of a
fabric prepared from a yarn of a blend fiber tends to decrease the
fluorine efficiency of the fabric. Heat treatment above Tg following
pressure dyeing has been observed to restore the fluorine efficiency. It
is also found that topical deposits such as processing oils and finishes,
such as those commonly employed in fiber spinning and fabrication of
textile goods, tend to mask the fluorinated surface, degrading the soil
repellency. Normal scouring, such as routinely performed in textile
dyeing and finishing, is effective at restoring the high degree of soil
repellency of yarns and fabrics prepared from the blend composition.

[0048] When a range of values is provided herein, it is intended to
encompass the end-points of the range unless specifically stated
otherwise. Numerical values used herein have the precision of the number
of significant figures provided, following the standard protocol in
chemistry for significant figures as outlined in ASTM E29-08 Section 6.
For example, the number 40 encompasses a range from 35.0 to 44.9, whereas
the number 40.0 encompasses a range from 39.50 to 40.49.

[0049] The parameters n, p, and q as employed herein are each
independently integers in the range of 1-10.

[0050] As used herein, the term "fluorovinyl ether functionalized aromatic
diester" refers to that subclass of compounds of structure (III), infra,
wherein R2 is C1-C10 alkyl. The term "fluorovinyl ether
functionalized aromatic diacid" refers to that subclass of compounds of
structure (III), infra, wherein R2 is H. The term "perfluorovinyl
compound" refers to the olefinically unsaturated compound represented by
structure (VII), infra. The term "fluorovinylether functionalized
aromatic polyester" refers to a polyester comprising a repeat unit as
depicted in structure I.

[0051] As used herein, the term "copolymer" refers to a polymer comprising
two or more chemically distinct repeat units, including dipolymers,
terpolymers, tetrapolymers and the like. The term "homopolymer" refers to
a polymer consisting of a plurality of repeat units that are chemically
indistinguishable from one another.

[0052] In any chemical structure herein, when a terminal bond is shown as
"--", where no terminal chemical group is indicated, the terminal bond
"--" indicates a radical. For example, --CH3 represents a methyl
radical.

[0053] In one embodiment, the first aromatic polyester is a
semi-crystalline polymer selected from the group consisting of
poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN),
poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof.
Semi-crystalline polymers have melting points. In the present disclosure,
the softening point in a process refers to the melting point of a
semi-crystalline first aromatic polyester.

[0054] In an alternative embodiment, the first aromatic polyester is an
amorphous polymer, such as copolymers comprising repeat units of
poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN),
poly(ethylene isophthalate), poly(trimethylene isophthalate) or
poly(butylene isophthalate). In such embodiment, there is no melting
point, and the softening point in the process can be determined according
to ASTM D1525-09, also known as the Vicat softening point. Suitable
amorphous polyesters include copolymers with such species as cyclohexane
dimethanol, or copolymers of terephthalic and isophthalic acid moieties.

[0055] In one aspect, the present invention provides a composition
comprising a first aromatic polyester selected from the group consisting
of poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate)
(PEN), poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof,
and a second aromatic polyester in contact therewith, wherein the second
aromatic polyester is present in the composition at a concentration; and,
wherein the second aromatic polyester comprises a molar concentration of
fluorovinylether functionalized repeat units represented by structure I

with the proviso that only one R can be OH or the radical represented by
the structure II; R1 is a C2-C4 alkylene radical which can
be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0056] a=0 or 1; and, Q represents the structure (Ia)

##STR00021##

wherein q=0-10; [0057] Y is O or CF2; [0058] Rf1 is
(CF2)n, wherein n is 0-10; [0059] and, [0060] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

[0061] In one embodiment, the first aromatic polyester is
poly(trimethylene terephthalate).

[0062] In one embodiment, the molar concentration of fluorovinylether
functionalized repeat units represented by structure I is in the range of
40-100 mol-%.

[0063] In one embodiment, the molar concentration of fluorovinylether
functionalized repeat units represented by structure I is in the range of
40-60 mol-%.

[0064] In one embodiment, the second aromatic polyester is present in the
composition at a concentration in the range of 0.1 to 10% by weight.

[0065] In a further embodiment, the second aromatic polyester is present
in the composition at a concentration in the range of 0.5 to 5% by
weight.

[0066] In a further embodiment, the second aromatic polyester is present
in the composition at a concentration in the range of 1 to 3% by weight.

[0067] In one embodiment the molar concentration of fluorovinylether
functionalized repeat units represented by structure I is in the range of
40-60 mol-%, and the second aromatic polyester is present in the
composition at a concentration in the range of 1 to 2% by weight.

[0068] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, each R is H.

[0069] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, one R is a radical represented by the
structure (II) and the remaining two Rs are each H.

[0070] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, R1 is an a trimethylene radical, which
can be branched or unbranched.

[0071] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, R1 is an unbranched trimethylene
radical.

[0072] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, X is O.

[0073] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, X is CF2.

[0074] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, Y is O.

[0075] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, Y is CF2.

[0076] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, Z is H.

[0077] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, Rf1 is CF2.

[0078] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, Rf2 is CF2.

[0079] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, p=0, and Y is CF2.

[0080] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, a=0.

[0081] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I a=1, q=0, and n=0.

[0082] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I, a=1, each R is H, Z is H, R1 is methoxy,
X is O, Y is O, Rf1 is CF2, and Rf2 is perfluoropropenyl,
and q=1.

[0083] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I the repeat unit is represented by the
structure (IVa)

##STR00022##

wherein R, R1, Z, X, Q, and a are as stated supra.

[0084] In one embodiment in the fluoroether functionalized repeat unit
represented by structure I the repeat unit is represented by the
structure (IVb)

##STR00023##

[0085] In one embodiment the second aromatic polyester further comprises
arylate repeat units represented by the structure (V),

##STR00024##

wherein each R is independently H or alkyl, and R3 is
C2-C4 alkylene which can be branched or unbranched, with the
proviso that when structure V is the condensation product of terephthalic
acid and an olefin, the alkylene radical is C3.

[0086] While there is no theoretical limitation on the molecular weight of
the second aromatic polyester, there is a practical benefit to employing
a second aromatic polyester with sufficient molecular mobility in the
melt to migrate to the surface of, e.g., a melt spun yarn. Number average
molecular weight in the range of 7,000-13,000 Da has been found to be
advantageous.

[0087] In another aspect, there is provided a process comprising combining
a first aromatic polyester selected from the group consisting of
poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN),
poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof,
with a second aromatic polyester to form a combination wherein the second
aromatic polyester is present in the combination at a concentration;
heating the combination to a temperature between the softening point of
the first aromatic polyester and the degradation temperature of at least
one component of the combination to form a viscous liquid mixture, and
mixing the viscous liquid mixture until it has achieved the desired
degree of homogeneity; the second aromatic polyester comprising a molar
concentration of fluorovinylether functionalized repeat units represented
by structure I

with the proviso that only one R can be OH or the radical represented by
the structure (II); R1 is a C2-C4 alkylene radical which
can be branched or unbranched;

X is O or CF2;

Z is H or Cl;

[0088] a=0 or 1; and, Q represents the structure (Ia)

##STR00027##

wherein q=0-10; [0089] Y is O or CF2; [0090] Rf1 is
(CF2)n, wherein n is 0-10; [0091] and, [0092] Rf2 is
(CF2)p, wherein p is 0-10, with the proviso that when p is 0, Y
is CF2.

[0093] In one embodiment of the process, the first aromatic polyester is
poly(trimethylene terephthalate).

[0094] In one embodiment of the process the second aromatic polyester is a
copolymer comprising a molar concentration of 40-100% of fluorovinylether
functionalized repeat units represented by structure I.

[0095] In one embodiment of the process, the second aromatic polyester is
combined with the first aromatic polyester at 0.1 to 10% by weight of the
total composition.

[0096] In a further embodiment, the second aromatic polyester is combined
with the first aromatic polyester at 0.5 to 5% by weight of the total
composition.

[0097] In one embodiment of the process, the second aromatic polyester
comprises a molar concentration of 40-50% of fluorovinylether
functionalized repeat units represented by structure I, and is combined
with the first aromatic polyester selected from the group consisting of
poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN),
poly(ethylene isophthalate), poly(trimethylene isophthalate),
poly(butylene isophthalate), mixtures thereof, and copolymers thereof at
1 to 2% by weight of the total composition.

[0098] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, each R is H.

[0099] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, one R is a radical represented by
the structure (II) and the remaining two Rs are each H.

[0100] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, R1 is an ethylene radical a
trimethylene radical, which can be branched or unbranched; or a
tetramethylene radical, which can be branched or unbranched.

[0101] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, R1 is an unbranched
trimethylene radical.

[0102] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, X is O.

[0103] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, X is CF2.

[0104] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, Y is O.

[0105] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, Y is CF2.

[0106] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, Z is H.

[0107] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, Rf1 is CF2.

[0108] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, Rf2 is CF2.

[0109] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, p=0, and Y is CF2.

[0110] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, a=0.

[0111] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I a=1, q=0, and n=0.

[0112] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I, a=1, each R is H, Z is H, R1
is methoxy, X is O, Y is O, Rf1 is CF2, and Rf2 is
perfluoropropenyl, and q=1.

[0113] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I the repeat unit is represented by
the structure (IVa)

##STR00028##

wherein R, R1, Z, X, Q, and a are as stated supra.

[0114] In one embodiment of the process, in the fluoroether functionalized
repeat unit represented by structure I the repeat unit is represented by
the structure (IVb)

##STR00029##

[0115] In one embodiment of the process, the second aromatic polyester
further comprises repeat units represented by the structure (V),

##STR00030##

wherein each R is independently H or alkyl, and R3 is
C2-C4 alkylene which can be branched or unbranched with the
proviso that when structure V is the condensation product of terephthalic
acid and an olefin, the alkylene radical is C3.

[0116] According to the process, mixing is continued until the desired
degree of homogeneity is achieved. The mixing end-point will depend upon
the requisites of any particular application. Mixing can be performed
both batch-wise and continuously. In batch mixing, one indicator of
homogeneity is the point at which the torque applied to the mixing tool
becomes constant. Suitable batch mixers include but are not limited to
Banbury internal mixers. In a continuous mixing process, homogeneity can
be evaluated by any suitable method including but not limited to
measuring variations in bulk density of the product stream, short or long
term variability of die pressure during strand extrusion, visual
observation of the extruded strand, or evaluation of production samples
under a microscope. Suitable continuous mixers include, but are not
limited to twin screw extruders, Farrel continuous mixers, and the like,
all well known in the art.

[0117] The second aromatic polyester comprising fluorovinylether
functionalized repeat units represented by structure I can be prepared by
a process comprising combining a fluorovinyl ether functionalized
aromatic diester or diacid with an excess of C2-C4 alkylene
glycol or a mixture thereof, branched or unbranched; and a catalyst to
form a reaction mixture. The reaction can be conducted in the melt,
preferably within the temperature range of 180 to -240° C., to
initially condense either methanol or water, after which the mixture can
be further heated, preferably to a temperature within the range of 210 to
-300° C., and evacuated, to remove excess C2-C4 glycol
and thereby form a polymer comprising repeat units having the structure
(I),

[0118] wherein the fluorovinyl ether functionalized aromatic diester or
diacid is represented by the structure (III),

with the proviso that only one R can be OH or the radical represented by
the structure (II); R2 is H or C1-C10 alkyl;

X is O or CF2;

Z is H, Cl, or Br;

[0119] a=0 or 1; and, Q represents the structure (Ia)

##STR00033## [0120] wherein q=0-10; [0121] Y is O or CF2; [0122]
Rf1 is (CF2)n, wherein n is 0-10; [0123] and, [0124]
Rf2 is (CF2)p, wherein p is 0-10, with the proviso
that when p is 0, Y is CF2. In some embodiments, the reaction is
carried out at about the reflux temperature of the reaction mixture.

[0125] In one embodiment of the process, one R is OH.

[0126] In one embodiment of the process, each R is H.

[0127] In one embodiment of the process, one R is OH and the remaining two
Rs are each H.

[0128] In one embodiment of the process, one R is represented by the
structure (II) and the remaining two Rs are each H.

[0129] In one embodiment of the process, R2 is H.

[0130] In one embodiment of the process, R2 is methyl.

[0131] In one embodiment of the process, X is O. In an alternative
embodiment, X is CF2.

[0132] In one embodiment of the process, Y is O. In an alternative
embodiment, Y is CF2.

[0133] In one embodiment of the process Z is Cl or Br. In a further
embodiment, Z is Cl. In an alternative embodiment, one R is represented
by the structure (II), and one Z is H. In a further embodiment, one R is
represented by the structure (II), one Z is H, and one Z is Cl.

[0134] In one embodiment of the process, Rf1 is CF2.

[0135] In one embodiment of the process, Rf2 is CF2.

[0136] In one embodiment of the process, Rf2 is a bond (that is,
p=0), and Y is CF2.

[0137] In one embodiment, a=0.

[0138] In one embodiment, a=1, q=0, and n=0.

[0139] In one embodiment of the process, each R is H, Z is Cl, R2 is
methyl, X is O, Y is O, Rf1 is CF2, and Rf2 is
perfluoropropenyl, and q=1.

[0140] Suitable alkylene glycols include but are not limited to
1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and mixtures thereof. In
one embodiment, the alkylene glycol is 1,3-propanediol.

[0141] Suitable catalysts include but are not limited to titanium (IV)
butoxide, titanium (IV) isopropoxide, antimony trioxide, antimony
triglycolate, sodium acetate, manganese acetate, and dibutyl tin oxide.
The selection of catalysts is based on the degree of reactivity
associated with the selected glycol. For example, it is known that
1,3-propanediol is considerably less reactive than is 1,2-ethanediol.
Titanium butoxide and dibutyl tin oxide--both considered "hot"
catalysts--have been found to be suitable for process when
1,3-propanediol is employed, but are considered over-active for the
process when 1,2-ethanediol.

[0142] The reaction can be carried out in the melt. The thus resulting
polymer can be separated by vacuum distillation to remove the excess of
C2-C4 glycol.

[0143] In one embodiment the reaction mixture comprises more than one
embodiment of the repeat units encompassed in structure (I).

[0144] In another embodiment, the reaction mixture further comprises an
aromatic diester or aromatic diacid represented by the structure (VI)

##STR00034##

wherein Ar is an aromatic radical, R4 is H or C1-C10
alkyl, and each R is independently H or C1-C10 alkyl. In a
further embodiment, R4 is H and each R is H. In an alternative
embodiment, R4 is methyl and each R is H. In one embodiment Ar is
benzyl. In an alternative embodiment, Ar is naphthyl.

[0145] Suitable aromatic diesters of structure (VI) include but are not
limited to dimethyl terephthalate, dimethyl isophthalate, 2,6-naphthalene
dimethyldicarboxylate, methyl 4,4'-sulfonyl bisbenzoate, methyl
4-sulfophthalic ester, and methyl biphenyl-4,4'-dicarboxylate. In one
embodiment, the aromatic diester is dimethyl terephthalate. In an
alternative embodiment, the aromatic diester is dimethyl isophthalate.
Suitable aromatic diacids of structure (VI) include but are not limited
to isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic
acid, 4,4'-sulfonyl bisbenzoic acid, 4-sulfophthalic acid and
biphenyl-4,4'-dicarboxylic acid. In one embodiment, the aromatic diacid
is terephthalic acid. In an alternative embodiment, the aromatic diacid
is isophthalic acid.

[0146] Suitable fluorovinyl ether functionalized aromatic diesters can be
prepared by forming a reaction mixture comprising a hydroxy aromatic
diester in the presence of a solvent and a catalyst with a perfluoro
vinyl compound represented by the structure (VII)

##STR00035##

wherein X is O or CF2, a=0 or 1; and, Q represents the structure
(Ia)

##STR00036## [0147] wherein q=0-10; [0148] Y is O or CF2; [0149]
Rf1 is (CF2)n, wherein n is 0-10; [0150]
Rf2 is (CF2)p, wherein p is 0-10, with the proviso
that when p is 0, Y is CF2; at a temperature between about
-70° C. and the reflux temperature of the reaction mixture.

[0151] Suitable perfluorovinyl ethers can range from perfluoromethyl vinyl
ether to PPPVE and larger perfluorovinyl ethers. It has been found that
PPVE and PPPVE are particularly suitable.

[0152] Preferably the reaction is conducted using agitation at a
temperature above room temperature but below the reflux temperature of
the reaction mixture. The reaction mixture is cooled following reaction.

[0153] When a halogenated solvent is employed, the group indicated as "Z"
in the resulting fluorovinyl ether aromatic diester represented by
structure (III) is the corresponding halogen. Suitable halogenated
solvents include but are not limited to tetrachloromethane,
tetrabromomethane, hexachloroethane and hexabromoethane. If the solvent
is non-halogenated Z is H. Suitable non-halogenated solvents include but
are not limited to tetrahydrofuran (THF), dioxane, and dimethylformamide
(DMF).

[0154] The reaction is catalyzed by a base. A variety of basic catalysts
can be used, i.e., any catalyst that is capable of deprotonating phenol.
That is, a suitable catalyst is any catalyst having a pKa greater than
that of phenol (9.95, using water at 25° C. as reference).
Suitable catalysts include, but are not limited to, sodium methoxide,
calcium hydride, sodium metal, potassium methoxide, potassium t-butoxide,
potassium carbonate or sodium carbonate. Preferred are potassium
t-butoxide, potassium carbonate, or sodium carbonate.

[0155] Reaction can be terminated at any desirable point by the addition
of acid (such as, but not limited to, 10% HCl). Alternatively, when using
solid catalysts, such as the carbonate catalysts, the reaction mixture
can be filtered to remove the catalyst, thereby terminating the reaction.

[0158] To prepare a suitable fluorovinyl ether functionalized aromatic
diester, a suitable hydroxy aromatic diester and a suitable perfluovinyl
compound are combined in the presence of a suitable solvent and a
suitable catalyst until the reaction has achieved the desired degree of
conversion. The reaction can be continued until no further product is
produced over some preselected time scale. The reaction time to achieve
the desired degree of conversion depends upon the reaction temperature,
the chemical reactivity of the specific reaction mixture components, and
the degree of mixing applied to the reaction mixture. Progress of the
reaction can be monitored using any one of a variety of established
analytical methods, such as, for example, nuclear magnetic resonance
spectroscopy, thin layer chromatography, and gas chromatography.

[0159] When the desired level of conversion has been achieved, the
reaction mixture is quenched, as described supra. The quenched reaction
mixture can be concentrated under vacuum, and rinsed with a solvent.
Under some circumstances, a plurality of compounds encompassed by the
structure (III) can be made in a single reaction mixture. In such cases,
separation of the products thus produced can be effected by any method
known to the skilled artisan such as, for example, distillation or column
chromatography.

[0160] If it is desired to employ the corresponding diacid as the monomer
instead of the diester, the thus produced fluorovinyl ether
functionalized aromatic diester can be contacted with an aqueous base,
preferably a strong base such as KOH or NaOH at a gentle reflux, followed
by cooling to room temperature, followed by acidifying the mixture,
preferably with a strong acid, such as HCl or H2SO4, until the
pH is between 0 and 2. Preferably pH is 1. The acidification causes the
precipitation of the fluorovinyl ether functionalized aromatic diacid.
The precipitated diacid can then be isolated via filtration and
recrystallization from suitable solvents (e.g., redissolved in a solvent
such as ethyl acetate, and then recrystallized). The progress of the
reaction can be followed by any convenient method, such as thin layer
chromatography, gas chromatography and NMR.

[0161] The blend composition is advantageously employed for the melt
spinning of fibers suitable for combination into textile and carpet
yarns. A variety of fibers can be spun from the composition. In one
embodiment, fibers and yarns of low denier per filament (dpf), especially
below 5 dpf, more especially in the range of 1 to 3 dpf, including both
spun-drawn and partially oriented fibers and yarns, are readily melt spun
from the blend compositions. The low dpf yarns are well-suited for use in
producing knitted and woven goods. In another embodiment, fibers and
yarns of high dpf, especially above higher than 10 dpf, more especially
in the range of 15 to 25 dpf, can be melt spun from the blend
compositions. The high dpf yarns are well-suited for production of
carpets and related goods. The high dpf fibers and yarns can be produced
as bulked continuous filament yarns (BCF) useful for the preparation of
carpet.

[0162] In a typical melt spinning process, several embodiments of which
are described infra, the dried polymer blend pellets are fed to an
extruder which melts the pellets and supplies the resulting melt to a
metering pump, which delivers a volumetrically controlled flow of polymer
into a heated spinning pack via a transfer line. The pump provides a
pressure of about 2-20 MPa to force the flow through the spinning pack,
which contains filtration media (e.g., a sand bed and a filter screen) to
remove any particles larger than a few micrometers. The mass flow rate
through the spinneret is controlled by the metering pump. At the bottom
of the pack, the polymer exits into an air quench zone through a
plurality of small holes in a thick plate of metal (the spinneret). While
the number of holes and the dimensions thereof can vary greatly,
typically a single spinneret hole has a diameter in the range of 0.2-0.4
mm. Spinning is advantageously accomplished at a spinneret temperature of
235 to 295° C., preferably 250 to 290° C. A typical flow
rate through a hole of that size tends to be in the range of 0.5-5 g/min.
Numerous cross-sectional shapes are employed for spinneret holes,
although circular cross-section is most common. Typically a highly
controlled rotating roll system through which the spun filaments are
wound controls the line speed. The diameter of the filaments is
determined by the flow rate and the take-up speed; and not by the
spinneret hole size.

[0163] The properties of filaments are determined by the threadline
dynamics, particularly in the quench zone that lies between the exit from
the spinneret and the solidification point of the filaments. The specific
design of the quench zone on the emerging still motile filaments affects
the quenched filament properties. Both cross-flow quench and radial
quench are in common use. After quenching or solidification, the
filaments travel at the take-up speed, that is typically 100-200 times
faster than the exit speed from the spinneret hole. Thus, considerable
acceleration (and stretching) of the threadline occurs after emergence
from the spinneret hole. The amount of orientation that is frozen into
the spun filament is directly related to the stress level in the filament
at the solidification point.

[0164] The melt spun filament thereby produced is collected in a manner
consistent with the desired end-use. For example, for filament intended
to be converted into staple fiber, a plurality of continuous filaments
can be combined into a tow that is accumulated in a so-called piddling
can. Filament intended for use in continuous form, such as in texturing,
is typically wound on a yarn package mounted on a tension-controlled
wind-up.

[0165] Staple fibers can be prepared by melt spinning the blend
composition into filaments, quenching the filaments, drawing the quenched
filaments, crimping the drawn filaments, and cutting the filaments into
staple fibers, preferably having a length of 0.2 to 6 inches (0.5 to 15
cm). One preferred process comprises: (a) melt spinning continuous
filaments of the blend composition at a spinneret temperature in the
range of 245 to 285° C., (b) drawing the quenched filaments, (c)
crimping the drawn filaments using a mechanical crimper at a crimp level
of 8 to 30 crimps per inch (3 to 12 crimps/cm), (d) relaxing the crimped
filaments at a temperature of 50 to 120° c., and e.g.) cutting the
relaxed filaments into staple fibers, preferably having a length of 0.2
to 6 inches (0.5 to 15 cm). In one preferred embodiment of this process,
the drawn filaments are annealed at 85 to 115° C. before crimping.
Preferably, annealing is carried out under tension using heated rollers.
In another preferred embodiment, the drawn filaments are not annealed
before crimping. Staple fibers are useful in preparing textile yarns and
textile or nonwoven fabrics, and can also be used for fiberfill
applications and making carpets.

[0166] FIG. 1 depicts one suitable arrangement for melt spinning according
to the invention. 34 filaments 102, (all 34 filaments are not shown) are
extruded through a 34-hole spinneret, 101. The filaments pass through a
quench zone 103, are formed into a yarn bundle, and passed over a finish
applicator 104. In the quench zone air is impinged upon the yarn bundle,
normally at room temperature and 60% relative humidity, at a typical
velocity of 40 feet/min. The quench zone can be designed for so-called
cross-air-quench wherein the air flows across the yarn bundle, or for
so-called radial quench wherein the air source is in the middle of the
converging filaments and flows radially outward over 360°. Radial
quench is a more uniform and effective quench method. Following the
finish applicator 104, the yarn is passed to a first driven godet roll
105, also known as a feed roll, set at 40 to 100° C., in one
embodiment, 70 to 100° C., coupled with a separator roll. The yarn
is wrapped around the first godet roll and separator roll 6 to 8 times.
From the first godet roll, the yarn is passed to a second driven godet
roll, also known as a draw roll, set at 110 to 170° C., coupled
with a second separator roll. The yarn is wrapped around the second godet
roll and separator roll 6 to 8 times. Draw roll speed is typically 1000
to 4000 m/min while the ratio of draw roll speed to feed roll speed is
typically in the range of 1.75 to 3.5. From the draw rolls, the yarn is
passed to a third driven godet roll 107, coupled with a third separator
roll, operated at room temperature and at a speed 1-2% faster than the
roll speed of the second godet roll. The yarn is wrapped around the third
pair of rolls 6 to 10 times. From the third pair of rolls, the yarn is
passed though an interlace jet 108, and then to a wind-up 109, operated
at a speed to match the output of the third pair of rolls.

[0167] Yarns formed from filaments made from the compositions disclosed
herein can contain other filaments as well. For example, a yarn can
contain other filaments of other polyesters, such as, for example
polyamides or polyacrylates, and other such filaments as may be desired.
The other filaments can optionally be staple fibers. The yarns, which can
be formed by the spun-draw process described supra and shown in FIG. 1,
or by other spinning processes well-known in the art, is suitable for use
as a feed yarn for false twist texturing as commonly practiced in order
to provide textile-like aesthetics to continuous polyester fibers.
Several types of texturing equipment are well-known in the art. The
texturing process comprises a) providing a yarn package as formed
according to the spinning process described supra; (b) unwinding the yarn
from the package, (c) threading the yarn end through a friction twisting
element or false-twist spindle, d) causing the spindle to rotate, thereby
imparting twist in the yarn upstream of the rotating spindle and,
downstream from the rotating spindle, untwisting the upstream twist,
along with the application of heat; and (e) winding the yarn onto a
package.

[0168] The fibers and yarns are suitable for preparation of fabrics and
carpets, as described supra. In one embodiment the filaments are bundled
into a plurality of yarns, and the fabric is a woven fabric. In an
alternative embodiment, the filaments are bundled into at least one yarn,
and the fabric is a knit fabric. In still another embodiment, the fabric
is a nonwoven fabric; in a further embodiment the nonwoven fabric is a
spunbonded fabric.

[0169] A nonwoven fabric, as used herein, is a fabric that is neither
woven nor knit. Woven and knit structures are characterized by a regular
pattern of interlocking yarns produced either by interlacing (wovens) or
looping (knits). Such yarns follow a regular pattern that takes them from
one side of the fabric to the other and back, over and over again. The
integrity of a woven or knitted fabric is created by the structure of the
fabric itself. In nonwovens, most commonly, filaments, typically extruded
simultaneously from a plurality of spinnerets, are laid down in a random
pattern and bonded to one another by chemical or thermal processes rather
than mechanical means. One commercially available example of a nonwoven
produced by is Sontara® Spun-Bonded Polyester available from the
DuPont Company. In some cases nonwovens can be produced by laying down
layers of fibers in a complex three dimensional topological array that
does not involve interlacing or looping and in which the fibers do not
alternate from one side to the other, as described in Popper et al., U.S.
Pat. No. 6,579,815.

[0170] Woven fabrics are made with a plurality of yarns interlaced at
right angles to each other. The yarns parallel to the length of the
fabric are called the "warp" and the yarns orthogonal to that direction
are called the "filling" or "weft." Variations in aesthetics can be
achieved by variations in the specific ways the yarns are interlaced, the
denier of the yarns, the aesthetics, both tactile and visual, of the
yarns themselves, the yarn density, and the ratio of warp to filling
yarns. As a general rule, the structure of a woven fabric imparts a
certain degree of rigidity to the fabric; a woven fabric does not in
general stretch as much as a knitted fabric.

[0171] In woven fabrics made using yarns of the blend compositions
disclosed herein, at least a portion of the warp comprises yarns
containing a filament comprising the blend composition. In one
embodiment, the aromatic polyester is poly(trimethylene terephthalate)
blend with F16-iso-50-co-tere, as defined supra. In one embodiment, both
the warp and fill contain a filament comprising the blend composition. In
one embodiment, the warp comprises at least 40% by number of yarns
comprising the filament comprising the blend composition and at least 40%
by number of cotton yarns. In one embodiment the warp comprises at least
80% by number of yarns comprising the filament comprising the blend
composition, and the fill comprises at least 80% cotton yarn. As a
general rule, there are greater physical demands placed upon warp yarns
than fill yarns.

[0172] Woven fabrics are fabricated on looms. FIG. 2a is a schematic
depiction of an embodiment of a loom, shown in side view. A warp beam,
201, made up of a plurality, often hundreds, of parallel ends, 202, is
positioned as the loom feed. Warp beam, 201, is shown in front view in
FIG. 2b. Shown in FIG. 2a is a two harness loom. Each harness, 204a, and
204b, is a frame that holds a plurality, often hundreds, of so called
"heddles." Referring to FIG. 2c, showing a front, blowup view of a
harness, 204, each heddle, 211, is a vertical wire having a hole, 312, in
it. The harnesses are disposed to move up or down, one moving up while
the other moves down. A portion of the ends, 203a, are threaded through
the holes, 212, in the heddles, 211, of upper harness, 204a, while
another portion of the ends, 203b, are threaded through the holes in the
heddles of lower harness, 204b, thereby opening up a gap between the ends
203a and 203b. In the type of loom shown, a shuttlecock, 206, is impelled
by means not shown--typically wooden paddles--to move or shuttle from
side to side as the harnesses move up and down. The shuttlecock carries a
bobbin of filler yarn, 207, that unwinds as the shuttlecock moves through
the gap in the warp ends. A "reed" or "batten," 205, is a frame that
holds a series of vertical wires between which the ends pass freely. FIG.
2d shows the reed, 205, in front view depicting the vertical wires, 213,
and the spaces between, 214, through which the warp yarns pass. The
thickness of the vertical wires, 214, determines the spacing of and
therefore density of warp yarns in the crossfabric direction. The reed
serves to push the newly inserted filler yarn to the right in the diagram
into place in the forming fabric, 208. The fabric is wound onto the
fabric beam, 210. The rolls, 209, are guide rolls.

[0173] The winding of a warp beam is a precision operation in which
typically the same number of yarn packages or spools as the desired
number of ends are mounted on a so-called creel, and each end is fed onto
the warp beam through a series of precision guides and tensioners, and
then the entire warp beam is wound at once.

[0175] Knitting is the process by which a fabric is prepared by the
interlooping of one or more yarns. Knits tend to have more stretch and
resilience than wovens. Knits tend to be less durable than wovens. As in
the case of wovens, there are many knit patterns, and styles of knitting.
In one embodiment, the fabric is a knit fabric comprising yarns
comprising a filament comprising the blend composition. In one
embodiment, the poly(trimethylene arylate) is poly(trimethylene
terephthalate).

[0176] In some embodiments, garments can be made from the fabrics. In one
embodiment, the poly(trimethylene arylate) is poly(trimethylene
terephthalate). The preparation of a garment from a fabric includes
preparing a pattern, usually from paper, or in computerized form for
automated processes, measuring the required fabric pieces, cutting the
fabric to prepare the needed pieces, and then sewing the pieces together
according to the pattern. Different styles of fabrics can be combined in
garments. In addition to fabrication of garments, the woven, knitted and
non-woven fabrics can be employed to fabricate tents, sleeping bags,
blankets, tarpaulins, and the like, using known techniques.

[0177] The repellency effect depends upon the surface concentration of
fluorine. While in no way intended to limit the scope of the invention,
it is speculated that the following five factors influence the surface
concentration of fluorine: [0178] The concentration of fluorine in the
fluorovinylether functionalized diester. At equal molar-concentrations,
it has been found that higher hexadecane contact angle was observed when
F16-iso was incorporated versus F10-iso, defined infra. [0179]
The concentration of the fluorovinylether functionalized comonomer in the
copolymer "additive." At similar loadings in the blend, using a higher
level of fluorine in the additive better repellency is achieved, [0180]
The concentration of the additive in the blend. For example, a 2 wt-%
concentration of 50 mol-% additive provides more repellency than a 1-wt-%
concentration of 50 mol-% additive. From the perspective of spinning
performance, it is in general desirable to use less of the second
aromatic polyester rather than more. [0181] The molecular weight of the
second aromatic polyester vis a vis that of the first aromatic polyester.
Presumably the lower the molecular weight of the additive, the more
rapidly it will diffuse to the surface at a given temperature. On the
other hand, lower molecular weight second aromatic polyester will have a
more deleterious effect on spinning performance than one that is higher
in molecular weight. [0182] The temperature/time/pressure history of the
melt and the fiber. Experimental results suggest that at atmospheric
pressure, heating to a temperature above Tg appears to increase
surface fluorine. Higher temperatures are associated with more rapid
diffusion. The longer the time, the more time for the molecules to
diffuse.

[0183] The invention is further described in the following specific
embodiments, but not limited thereto.

EXAMPLES

Materials

[0184] Purchased from Aldrich Chemical Company, and used as received, were

[0194] Electron Spectroscopy for Chemical Analysis (ESCA) was performed
using an Ulvac-PHI Quantera SXM spectrometer with a monochromatic Al
X-ray source (100 μm, 100 W, 17.5 kV). The sample surface (˜1350
μm×200 μm) was first scanned to determine the elements that
were present on the surface. High resolution detail spectral acquisition
using 55 eV pass energy with a 0.2 eV step size was acquired to determine
the chemical states of the detected elements and their atomic
concentrations. Typically carbon, oxygen, and fluorine were analyzed at
45° exit angle (˜70 Å escape depth for carbon
electrons). PHI MultiPak software was used for data analysis.

[0195] Surface contact angles were recorded on a. Rame'-Hart Model
100-25-A goniometer (Rame'-Hart Instrument Co) with an integrated
DROPimage Advanced v2.3 software system. A micro syringe dispensing
system was used for either water or hexadecane. A volume of 4 μL of
liquid was used.

[0196] The surface tension of yarn and fabric samples was estimated on a
relative basis as follows: The specimen was conditioned for 4 hours at
21° C. and 65% relative humidity, after which it was placed on a
flat level surface.

[0197] Three drops of each of a series of water/ispropanol solutions
listed in Table 1 were placed on the surface of the specimen and left for
10 seconds, starting with solution number 1. If no wicking was observed
to have occurred to the naked eye, the fabric was rated to have "passing"
repellency for that solution. Then the next higher numbered solution was
applied. The rating of the test specimen represented the highest numbered
solution that did not wick into the test specimen. The surface tension of
the solutions decreased with increasing solution number. The lower the
surface tension of a liquid that fails to wick into the test specimen,
the lower the surface tension of the test specimen.

[0199] Yarn accelerated soil testing was measured according to a modified
version of AATCC 123-2000. The method is based upon visual matching under
standard lighting of the test specimen with a gray scale. To determine
gray scale rating, the specimen was illuminated using a Visual Gray Scale
Light Box (Cool White Fluorescent) at a 45° angle. The gray scale
rating ranges from 0-5 (5 being excellent, 0 being poor). In the method
employed, a 7 cm×10 cm Q-panel aluminum test panel (available from
Q-Lab Corporation) was wrapped with about 4 g of the yarn test specimen
to cover an area of ca. 6 cm×7 cm. The thus prepared test panel was
inserted into diametrically opposed slots along the internal wall of a 74
mm diameter, 126 mm high cylindrical canister, thereby dividing the
canister into two compartments. Into each compartment thus formed were
inserted 71 g of stainless steel 5/16'' diameter ball bearings, and 10 g
of pre-soiled 1/8'' nylon pellets (soiled according to AATCC 123-1995).
The canister was then sealed closed and placed on a lab bench scale mini
drum roller configured to rotate the canister about its cylindrical axis.
The canister was rotated at 140 rpm for 2.5 minutes. It was then rotated
180° C. about the vertical axis normal to the cylindrical axis
thereof (in simple terms, the canister was turned head to tail) and was
then rolled for an additional 2.5 minutes at 140 RPM. The test specimen
was then removed, the surface thereof cleaned with a vacuum cleaner and
evaluated by visual (gray scale) observation.

[0201] Glass transition temperature (Tg) and melting point (Tm)
were determined by differential scanning calorimetry (DSC) performed
according to ASTM D3418-08.

Mechanical Properties

[0202] Fiber tenacity was measured on a Statimat ME fully automated
tensile tester. The test was run according to an automatic static tensile
test on yarns with a constant deformation rate according to ASTM D 2256.

[0204] In a nitrogen purged dry box, THF (500 mL) and dimethyl
5-hydroxy-isophthalate (42 g, 0.20 mol) were added to an oven-dried round
bottom reaction flask equipped with a stirrer and addition funnel.
Potassium carbonate catalyst (6.955 g, 0.0504 mol) was added via the
addition funnel to form a reaction mixture. Subsequently PPVE (79.8 g,
0.30 mol) was added via the addition funnel and the thus formed reaction
mixture was heated to reflux at 66° C. for 16 hours. The catalyst
was then removed from the resulting mixture via filtration through a bed
of silica gel. The filtrate thus produced was concentrated under vacuum
using a rotary evaporator, followed by vacuum distillation to give 81.04
g (85.12% yield) of the desired dimethyl
5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate
(F10-iso) collected as the distillate.

[0206] Dimethylterephtalate (12.2 g, 63 mmol), dimethyl
5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophtalate (30 g, 63
mmol), and 1,3-propanediol (17.25 g, 0.226 mol) were charged to a
pre-dried 500 mL three necked round bottom flask fitted with an overhead
stirrer and a distillation condenser. A nitrogen purge was applied to the
flask which was at 23° C., and stirring was commenced at 50 rpm to
form a slurry. While stirring, the flask was evacuated to 100 torr and
then repressurized with N2, for a total of 3 cycles. After the first
evacuation and repressurization, 13 mg of Tyzor® titanium (IV)
isopropoxide available from the DuPont Company was added.

[0207] After the 3 cycles of evacuation and repressurization, the flask
was immersed into a preheated liquid metal bath set at 160° C. The
contents of the flask were stirred for 20 minutes after placing it in the
liquid metal bath, causing the solid ingredients to melt, after which the
stirring speed was increased to 180 rpm and the liquid metal bath
setpoint was increased to 210° C. After about 20 minutes, the bath
had come up to temperature. The flask was then held at 210° C.
still stirring at 180 rpm for an additional 45-60 minutes to distill off
most of the methanol being formed in the reaction. Following the hold
period at 210° C., the nitrogen purge was discontinued, and a
vacuum was gradually applied in increments of approximately -10 torr
every 10 seconds while stirring continued. After about 60 minutes the
vacuum leveled out at 50-60 mtorr. The stirring speed was then increased
to 225 rpm, and the conditions maintained for 3 hours.

[0208] Periodically, the stirring speed was reduced to 180 rpm, and then
the stirrer was stopped. The stirrer was restarted, and the applied
torque about 5 seconds after startup was measured. When a torque of 25
N/cm or greater was observed, reaction was discontinued by halting
stirring and removing the flask from the liquid metal bath. The overhead
stirrer was elevated from the floor of the reaction vessel and then the
vacuum was turned off and the system purged with N2 gas. The thus
formed copolymer product was allowed to cool to ambient temperature and
the product recovered after carefully breaking the glass with a hammer.
Yield ˜90%. Tg was ca. 34° C. 1H-NMR (CDCl3)
δ: 8.60 (ArH, s, 1H), 8.15-8.00 (ArH--, m, 2+4H), 7.65 (ArH, s,
4H), 6.15 (--CF2--CFH--O--, d, 1H), 4.70-4.50 (COO--CH2--, m,
4H), 3.95 (--CH2--OH, t, 2H), 3.85 (--CH2--O--CH2--, t,
4H), 2.45-2.30 (--CH2--, m, 2H), 2.10
(--CH2--CH2--O--CH2--CH2--, m, 4H).

[0211] The F10-iso-50-co-tere copolymer so prepared was chopped into
one inch sized pieces that were placed in liquid nitrogen for 5-10
minutes, followed by charging to a Wiley mill fitted with a 6 mm screen.
The sample was milled at ca. 1000 rpm to produce coarse particles
characterized by a maximum dimension of about 1/8''. The particles so
produced were dried under vacuum and allowed to warm to ambient
temperature.

[0212] D. Preparation of a Polymer Blend

[0213] Sorona® Bright (1.02 dl/g IV) poly(trimethylene terephthalate)
(PTT) pellets available from the DuPont Company were dried overnight in a
vacuum oven at 120° C. under a slight nitrogen purge. The
F10-iso-50-co-tere copolymer particles prepared in Section C above
were dried overnight in a vacuum oven at ambient temperature under a
slight nitrogen purge. Prior to melt compounding the thus dried pellets
were combined together to form a first batch with a concentration of 1
wt-% of the F10-iso-50-co-tere copolymer in the PTT (Example 1), and
a second batch with a concentration of 2 wt-% of the
F10-iso-50-co-tere copolymer in the PTT (Example 2). Each batch so
prepared was mixed in a plastic bag by shaking and tumbling by hand.

[0214] Each thus mixed batch was placed into a K-Tron T-20 (K-Tron Process
Group, Pittman, N.J.) weight loss feeder feeding a PRISM laboratory
co-rotating twin screw extruder (available from Thermo Fisher Scientific,
Inc.) equipped with a barrel having four heating zones and a diameter of
16 millimeter fitted with a twin spiral P1 screw. The extruder was fitted
with a 1/8'' diameter circular cross-section single aperture strand die.
The nominal polymer feed rate was 3-51 bs/hr. The first barrel section
was set at 230° C. and the subsequent three barrel sections and
the die were set at 240° C. The screw speed was set at 200 rpm.
The melt temperature of the extrudate was determined to be 260° C.
by inserting a thermocouple probe into the melt as it exited the die. The
thus extruded monofilament strand was quenched in a water bath.

[0215] Air knives dewatered the strand before it was fed to a cutter that
sliced the strand into ˜2 mm length blend pellets.

[0216] E. Spinning 20 Denier Per Filament Multifilament Yarn

[0217] The blend pellets formed in section D were then melt spun into
spun-drawn fibers. The blend pellets were fed using a K-Tron weight loss
feeder to a 28 millimeter diameter twin screw extruder operating at ca.
30-50 rpm to maintain a die pressure of 600 psi. A Zenith metering pump
conveyed the melt f to the spinneret at a throughput rate of 29.9 g/min.
Referring to FIG. 3 the molten polymer from the metering pump was forced
through a 4 mm glass bead screen to a 10 hole spinneret, 301, heated to
265° C. Each orifice was shaped to provide a filament with a
modified delta-type cross section. The specific geometry of the spinneret
orifice is described in FIG. 1 of U.S. Published Patent Application
2010/0159186 and the accompanying description. The filamentary streams
leaving the spinneret, 302, were passed into an air quench zone, 303,
where they were impinged upon by a transverse air stream at 21° C.
The filaments were then passed over a spin finish head, 304, where a spin
finish was applied, and the filaments were converged to form a yarn. The
yarn so formed was conveyed via a tensioning roll, 305, onto two feed
rolls (godets), 306, heated to 55° C. and spinning at 500 rpm and
then onto two draw rolls (godets), 307, heated to 160° C. and
spinning at 1520 rpm. From the draw rolls, 307, the filaments were passed
onto two pair of let-down rolls, 308, operating at ambient temperature
and collected on a winder, 309, at 1520 rpm. The extruder was provided
with 9 barrel sections of which the first section was kept at 150°
C. and the subsequent sections at 255° C. The spinneret pack (top
and band) was set at 260° C. and the die at 265° C. Results
are shown in Table 2. A control sample, Comparative Example A (CE-A) of
unblended Sorona® Bright was also spun into fiber.

[0218] The fibers so prepared were particularly well-suited for use in the
preparation of carpets.

[0220] The procedures of Example 1 section A were repeated except that
129.6 g of PPPVE were employed in place of the PPVE of Example 1 section
A. 123.39 g (96.10% yield) of the desired product, (dimethyl
5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)-
ethoxy)isophthalate (F16-iso) were collected as the distillate.

[0222] Dimethylterephtalate (36.24 g, 0.187 mmol), F16-iso (120 g,
0.187 mol), and 1,3-propanediol (51.2 g, 0.672 mol) were charged to a
pre-dried 500 mL three necked round bottom flask fitted with an overhead
stirrer and a distillation condenser. A nitrogen purge was applied to the
flask which was at 23° C., and stirring was commenced at 50 rpm to
form a slurry. While stirring, the flask was evacuated to 100 torr and
then repressurized with N2, for a total of 3 cycles. After the first
evacuation and repressurization, 48 mg of Tyzor® titanium (IV)
isopropoxide was added.

[0226] The milling procedures of Example 1 section C were replicated. The
particles so produced were dried under vacuum and allowed to warm to
ambient temperature.

[0227] D. The methods of Example 1 section D were replicated to form the
melt blend of Sorona® Bright (I.V.=1.02 dl/g) with the
F16-iso-50-co-tere. Blends of 1 (Example 3) and 2 (Example 4) wt-%
concentration were formed as in Example 1.

[0228] E. The blend pellets prepared in Examples 3 and 4 section D above
were fed to the 28 mm extruder, as in Example 1. The procedures of
Example 1 Section E were replicated to form 10 filament, approximately 20
dpf yarns. Conditions that differed from Example 1 are shown in Table 3.
A sample of Sorona® Bright with no fluorovinylether isophthalate
copolymer added was used as Comparative Example B (CE-B). Tensile test
results are shown in Table 4.

[0229] The yarns so produced had particular utility for the preparation of
carpets.

[0230] About 6.5 g of the yarn of Example 4 was back wound to a stainless
steel wire mesh bobbin at 150 rpm. The so collected yarn was scoured
three times in 65-70° C. heated water for 5 minutes (water was
replaced between each scour) and subsequently dried for 30 minutes at
50° C. and allowed to air dry for 48 hours prior to soil
evaluation. Soil repellency was then determined according to the method
described supra. Results comparing the yarn of CE-B with that of Example
4, scoured and unscoured, are shown in Table 5.

[0231] ESCA was also used to determine the surface concentration of
fluorine in the test yarns. With the exit angle set at 45° the
fluorine content of the scoured yarn of Example 4 was found to be 4.6
atom-%--more than 10 times the calculated bulk concentration. Results are
shown in Table 5. Note that ESCA was not performed on CE-B. Since the
control had no fluorine in it to begin with, it is assumed that there
would be no detectable amount on the surface.

[0232] Steps A-D of Example 3 were repeated to produce two batches of
blends of the F16-iso and Sorona Bright prepared as described in
Example 3, one with 1% by weight of F16-iso-50-co-tere (Example 5)
and one with 2% by weight of F16-iso-50-co-tere (Example 6).

[0233] Each blend was melt spun into yarn following the procedures of
Example 3 Section E except that the spinneret had 34 holes each of
circular cross-section, 0.010 inches in. diameter×0.040 inches in
length. A sample of unblended Sorona® Bright was used as a control
(CE-C). Spinning conditions are shown in Table 6. Mechanical properties
of the yarns are shown in Table 7.

[0234] The yarns so produced are particularly suitable in the preparation
of knit, woven, and non-woven textile goods.

[0236] B. Dimethylterephtalate (DMT, 130 g, 0.66 mol), F10-iso (6.5
g, 13.6 mmol, 5 wt-% to DMT or 2 mol %), and 1,3-propanediol (90.4 g,
1.19 mol) were charged to a pre-dried 500 mL three necked round bottom
flask. An overhead stirrer and a distillation condenser were attached.
The reactants were stirred under a nitrogen purge at a speed of 50 rpm.
The condenser was kept at 23° C. The contents were degassed three
times by evacuating to 100 torr and refilling back with N2 gas. 42
mg of titanium(IV) isopropoxide catalyst was added after the first
evacuation. The flask was immersed into a preheated metal bath set at
160° C. The solids were allowed to completely melt with stirring
at 160° C. for 20 minutes after which the stirring speed was
slowly increased to 180 rpm. The temperature set-point was increased to
210° C. and maintained for 90 minutes to distill off most of the
formed methanol. The temperature set-point was then increased to
250° C. after which the nitrogen purge was closed and a vacuum
ramp started. After about 60 minutes the vacuum reached a value of 50-60
mtorr. As the vacuum stabilized the stirring speed was increased to 225
rpm and the reaction held for 4 hours. The torque was monitored as
described in Example 1 and the reaction was typically stopped when a
value of 100 N/cm2 or greater was reached. The polymerization was
stopped by removing the heat source. The over head stirrer was elevated
from the floor of the reaction vessel before the vacuum was turned off
and the system purged with N2 gas. The product was recovered after
carefully breaking the glass with a hammer. Tg was ca. 51°
C., Tm was ca. 226° C. IV was ca. 0.88 dL/g.

[0237] Step C was the same as in Example 1.

[0238] D. Referring to FIG. 4, the cryogenically milled particles of
polymer, 401, were charged to a steel cylinder, 402, and topped of with a
Teflon® PTFE plug, 403. A hydraulically driven piston, 404,
compressed the particles, 401, into a melting zone provided with a heater
and heated to 260° C., 405, where a melt, 206, was formed, and the
melt then forced into a separately heated, 407, round cross-section
single-hole spinneret, 408, heated to 265° C. Prior to entering
the spinneret, the polymer passed through a filter pack, not shown. The
melt was extruded into a single strand of fiber, 409, 0.3 mm in diameter
at a rate of 0.9 g/min. The extruded fiber was passed through a
transverse air quench zone, 410, and thence to a wind-up, 411, operated
at 500 m/min take-up speed. A control fiber of Sorona® Bright was
also spun under identical conditions. In general, single filaments were
produced for 30 minutes and in each case the filament spun smoothly
without breaks. The resulting fiber was flexible and strong as determined
by pulling and twisting by hand.

Examples 8

[0239] Step A was the same as in Example 2.

[0240] B. The procedures and materials and weights of materials of Example
7 employed for forming the copolymer with DMT and 1,3-propanediol were
followed, except that 6.5 g of F16-iso of Step A above was
substituted for the 6.5 g of F10-iso in Example 7. Tg was ca.
51° C., Tm was ca. 226° C. IV was ca. 0.86 dL/g.

[0241] Step C was the same as in Example 1.

[0242] D. The melt press spinning procedures of Example 7 were repeated
exactly except that the F16-iso-1.5-co-tere particles prepared in
Step C above were employed. The resulting fiber was flexible and strong
as determined by pulling and twisting by hand.

[0244] B. DMT (1080 g), the F16-iso (3572 g) prepared in Section A
above, 1,3-propanediol (1521 g), and titanium (IV) isopropoxide (2.83 g)
were charged to a 10-lb stainless steel stirred autoclave (Delaware
valley steel 1955, vessel #: XS 1963) equipped with a stirring rod and
condenser. A nitrogen purge was applied and stirring was commenced at 50
rpm to form a slurry. While stirring, the autoclave was subject to three
cycles of pressurization to 50 psi of nitrogen followed by evacuation. A
weak nitrogen purge (˜0.5 L/min) was then established to maintain
an inert atmosphere. While the autoclave was heated to the set point of
225° C. methanol evolution began at a batch temperature of
185° C. Methanol distillation continued for 120 minutes during
which the batch temperature increased from 185° C. to 220°
C. When the temperature leveled out at 220° C., a vacuum ramp was
initiated that during 60 minutes reduced the pressure from 760 torr to
300 torr (pumping through the column) and from 300 torr to 0.05 torr
(pumping through the trap). The mixture, when at 0.05 torr, was left
under vacuum and stirring for 5 hours after which nitrogen was used to
pressurize the vessel back to 760 torr. The formed polymer was recovered
by pushing the melt through an exit valve at the bottom of the vessel.
Yield was ca. 10 lbs (ca. 95. Tg was ca. 24° C. 1H-NMR
(CDCl3) δ: 8.60 (ArH, s, 1H), 8.15-8.00 (ArH--, m, 2+4H), 7.65
(ArH, s, 4H), 6.15 (--CF2--CFH--O--, d, 1H), 4.70-4.50
(COO--CH2--, m, 4H), 3.95 (--CH2--OH, t, 2H), 3.85
(--CH2--O--CH2--, t, 4H), 2.45-2.30 (--CH2--, m, 2H), 2.10
(--CH2--CH2--O--CH2--CH2--, m, 4H).

[0245] C. Sorona® Semi Bright (1.02 dl/g IV) PTT pellets were dried
overnight in a hopper at 120° C. under a slight nitrogen purge.
The F16-iso-50-co-tere copolymer prepared in Section B above was cut
into rectangular slabs (2.5×2.5×20 cm) and dried overnight in
a vacuum oven at ambient temperature under a slight nitrogen purge.
Pellets of neat Sorona® Semi bright (1.02 dL/g?) were weight-loss fed
to a 28/30 mm co-rotating twin screw extruder equipped with 9 barrel
segments. To barrel section #4 was attached the output of a Bonnet single
screw melt feeder which metered the F16-iso-50-co-tere copolymer
into the twin screw extruder. The temperature of the Bonnet feeder was
kept at 150° C. and the rate of feed set at position #2. The feed
rates were adjusted to yield a master batch blend of 20 wt-% of
F16-iso-50-co-tere in the Sorona® Semi bright melt. The
resulting melt blend was extruded through a circular cross section 1/4''
diameter single aperture strand die. The nominal polymer throughput rate
was 30-50 lbs/hr.

[0246] The first barrel section of the extruder was set at 230° C.,
the subsequent three barrel sections set at 240° C., the
subsequent barrel section set at 230° C., the subsequent three
barrel sections and the die were set at 225° C. The screw speed
was set at 250 rpm. The extruded monofilament strand was quenched in a
water bath. Air knives dewatered the strand before it was fed to a cutter
that sliced the strand into ˜2 mm length blend pellets.

[0248] D. The blend pellets formed in section C were then melt spun into
bulked continuous filament (BCF) yarn that is particularly well-suited
for preparation of carpets. In Examples 9, 10, and 11, neat Sorona®
Semi-Bright was placed into one weigh-loss feeder, and the masterbatch
prepared as described supra was placed into another weight loss feeder.
The two weight-loss feeders fed their respective pellets to the feed
throat of a single screw spinning extruder at the feed ratios to provide
a melt having 1,2, and 4 wt-% respectively of the F16-iso-50-co-tere, and
this melt was extruded into fibers, as described infra. In Example 12,
the masterbatch and the neat sorona were first melt blended in a twin
screw extruder to produce a pelletized blend of 2 wt-%
F16-iso-50-co-tere. Those 2 wt-% blend pellets were then fed to the
single screw spinning extruder.

[0249] FIG. 5 is a schematic diagram of a spinning arrangement for
manufacturing of the bulked continuous filaments. Polymer blend pellets
prepared in C above were fed individually (Example 12), or from the
master batch in combination with neat Sorona Semi Bright (Examples 9, 10
and 11) into a 45 mm single screw extruder with four heat zones of which
zone 1 was kept at 255° C. and zones 2-4 kept at 260° C.
and the thus formed melt pumped via gear pump through a spin pack
assembly, 500, that included a spinneret, 501, plate having 70 orifices
designed to produce filaments with modified delta cross-sections, as
described supra. The spin pack assembly also contained a filtration
medium. Filaments, 502, were spun when polymer was extruded through the
spinneret plate and filaments are pulled through a quench, 503, chimney
(air with ca. 77% relative humidity) by feed rolls, 504,. Finish, 505, is
applied to the filaments by a finish roll located upstream from the feed
rolls. The feed rolls were set at 60° C. From the feed rolls, the
yarn was passed to draw rolls, 306, heated to 150° C. Air heated
to 200° C. was impinged by bulking jet, 507. The resulting bulked
filaments were laid on a rotating stainless steel drum 508 heated to
80° C. having a perforated surface. The filaments were cooled
under zero tension by pulling air through them using a vacuum pump, 509,.
After the filaments were cooled the filaments were pulled off the drum,
510 . . . . The filament bundle was interlaced, 512, periodically by an
interlacing jet disposed between a pull roll 513, and a let down roll,
514, and collected by a winder, 515.

[0250] Conditions are shown in Table 8 below. A sample of Sorona®
Bright with no fluorovinylether isophthalate copolymer added was used as
Comparative Example D (CE-D). Tensile test results are shown in Table 9
below.

[0251] Steps A-D was the same as in Example 9 above. The produced BCF yarn
was back wound onto 48 cones. The yarn that was prepared in Examples 9-12
and Comparative Example D was back wound onto 48 cones each. Back winding
was done on each individual set of yarn of Ex. 9, 10, 11, 12, above, and
CE D by running the cones on a cone winder for 3-5 minutes at 100 m/min
to transfer ˜300-500 m from the main bobbin onto each individual
cone. Tufting was done on a 48 end Venor tufting machine (Daniel Almond
Ltd., Union Works, Waterfront, Lancashire, England). At least 10 inches
of yarn was pulled through each needle so that the tension could be kept
during start up. The backing (36'' 18 PK beige PolyBac from Propex) was
inserted under the needles and through the top and bottom feed rollers.
While holding tension of the threaded yarn the treadle was engaged by a
foot pedal connected with the motor. After release of the yarn, the
backing was manually guided from its edges. When the desired length was
complete the foot pedal was released and the thus prepared sample cut,
initial pass ˜3.5×50''. The obtained carpet sample was white
in color, soft and with a basis weight of ca. 1090 g/m2.

Example 14 and Comparative Example E

[0252] Knitted hose leg samples were produced from the yarn of Example 6
and CE-C on a FAK (Lawson-Hemthill) circular knitting machine. A 75 gage
needle was used, 380 heads, and with 35 needles/inch using a low
throughput.

[0253] The knitted samples were dyed blue using an Atlas LP-1
Laundrometer, Book centrifugal extractor, and Whirlpool automatic dryer.
For the dyeing bath, water (30×mass of fabric) and disperse Blue 27
dyestuff (2 wt-% relative to the weight of fabric) was charged in a steel
can vessel and the pH adjusted to 4.5-5 using acetic acid. The fabric was
added and the can placed in the Laundrometer which was sealed using a lid
with rubber and Teflon gaskets. The Laundrometer was run for 30 minutes
at 121° C. The fabric was removed, rinsed in hot water,
centrifuged to extract the excess water, and dried in the automatic
dryer.

[0254] Water and oil repellency of the blue dyed knitted fabric were
characterized using the method described, supra. The neat PTT fiber
control was compared with a fabric prepared from the yarn of Example 6
containing at 2 wt-%. One specimen of each fabric was subject to a
post-dyeing heat treatment at 121° C. for 20 minutes. Results are
summarized in the Table 10:

[0255] The yarns of Example 5, 6 and Comparative Example C were woven in a
2×1 twill samples were prepared on a CCI sample weaving system with
integrated sizing, warping and weaving. Sizing was performed by running
the yarn through a 50/50 volume-% water/polyvinyl alcohol bath and
subsequently dried over heated air (T=80° C.). The warp was made
by applying the yarn around a 5 yard circumference (20'' wide) warp drum.
The warp was taken off the drum, cut and mounted on a flat tape lease.
The ends were drawn into a single heddle eye and into the reed. The
weaving pattern was now drawn into the loom, i.e. the warp drum, harness
and reed were placed in the loom and the weaving conducted . . . . The
fabric thus produced was taken up on a take up roll.

[0256] The as-made woven sample was scoured to remove the PVA sizing. The
sample was scoured three times in heated 65-70° C. water for 5
minutes (water was replaced between each scour) and subsequently dried
for 30 minutes at 50° C. and allowed to air dry for 48 hours prior
to water repellency evaluation. The water repellency performance of the
thus scoured fabric was characterized according to the method described
supra. Results are shown in Table 11.

[0257] The yarns of Example 5, 6 and Comparative Example C were used to
produce knitted samples on a Mayer CIE OVJ 1.6E3 wt 18 gauge Jacquard
Double Knit, 34 feeds. The stitch number on the cylinder needles was set
at 12. The stitch number on the dial needles was set at 12. The Dial
height was 1.5 mM. The timing was 4 needles advance. The packages were
broken down on a back winder and a very small stitch was pulled. The
soft, off-white 300×82 cm fabric produced had good stretch with a
basis weight of 130 g/m2.